JP2009001730A - Polymer compound and production method thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a self-photocuring polymer compound, which can be used for curing by active energy such as ultraviolet ray with efficient photocuring property, and can minimize odor during the polymerization curing reaction and thus suppress deterioration of the working environment. <P>SOLUTION: The polymer compound includes one or more compound residues represented by the general formula and one or more ethylenic unsaturated double bonds in one molecule. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a novel polymer compound that can be self-photocured by active energy such as ultraviolet rays, and is particularly excellent in hardness, adhesion, chemical resistance, and active energy ray-curable coating material that can be cured in a short time, ink, coating agent, etc. The present invention relates to a suitable high molecular compound and a novel compound used for the synthesis thereof.

Compared to paints, coatings, inks, etc. that cure by conventional epoxy resin, melamine resin and other thermosetting resins due to light irradiation such as ultraviolet rays, energy saving, space saving, short time curing, and film strength In particular, it can be widely applied to applications requiring surface hardness, scratch resistance and chemical resistance as a protective coating agent.
A conventional photocurable resin is generally a solventless type in which a photocurable monomer or an oligomer, a photopolymerization initiator, and a dilution monomer for viscosity adjustment are mixed. However, there are problems such as large volume shrinkage during curing and low adhesion. Further, it is not appropriate in the recent environmental problems in terms of odor and toxicity due to volatilization of monomers, photopolymerization initiators, and decomposition products thereof.

As a solution to this problem, it has been proposed to use a polymerized photopolymerization initiator (Patent Document 1 and Patent Document 2). However, these polymerizations require a plurality of synthesis steps and are not easy to manufacture. Patent Document 3 discloses a photopolymerization initiator having a high molecular weight that does not require a plurality of synthesis steps. For the photopolymerization initiator having a high molecular weight, a photopolymerizable monomer or oligomer is used. Since they are not present in one molecule but are present separately, photocurability is not efficient, and unreacted high molecular weight photopolymerization initiator remains and volatilizes from the cured product or from the cured product. There was a problem that odor was generated and the working environment was deteriorated.
JP-A-10-279894 JP 2002-187906 A JP 2006-28463 A

  In view of the above-mentioned problems of the conventional photopolymerization initiator, the present invention can be used for curing by active energy such as ultraviolet rays, has high photocurability, and generates very little odor during polymerization curing reaction. Another object of the present invention is to provide a self-photocurable polymer compound that can suppress deterioration of the working environment.

で示される化合物。ここでＲ_１、Ｒ_２及びＲ_３はそれぞれ独立に炭素数１〜４のアルキル基を表わし、ｍ、ｎは１〜３の整数である。 As a result of intensive studies to solve the above problems, the present inventors have completed the present invention.
That is, the present invention is as follows.
(1) The following general formula (a)

A compound represented by Here, R ₁ , R ₂ and R ₃ each independently represents an alkyl group having 1 to 4 carbon atoms, and m and n are integers of 1 to 3.

ここでＲ_１、Ｒ_２及びＲ_３はそれぞれ独立に炭素数１〜４のアルキル基を表わし、ｍ、ｎは１〜３の整数である。
（３）上記高分子化合物の重量平均分子量が５０００〜１００００００である上記（２）に記載の高分子化合物。 (2) A polymer compound containing one or more residues of a compound represented by the following general formula (b) and one or more ethylenically unsaturated double bonds in one molecule.

Here, R ₁ , R ₂ and R ₃ each independently represents an alkyl group having 1 to 4 carbon atoms, and m and n are integers of 1 to 3.
(3) The polymer compound according to (2), wherein the polymer compound has a weight average molecular weight of 5,000 to 1,000,000.

(4) In the above molecule (1), the residue of the compound represented by the general formula (b) is a photosensitizing functional group that generates radicals by active energy rays, and the polymer compound is a self-photocurable resin ( The polymer compound according to 2) or (3).
(5) An ethylenically unsaturated monomer (C) obtained by an addition reaction between a hydroxyl group-containing benzoyl compound (A) and an isocyanate group-containing ethylenically unsaturated monomer (B), containing a reactive functional group An addition reaction with (D) is possible on a copolymer obtained by copolymerizing an ethylenically unsaturated monomer (D) and a mixture of other ethylenically unsaturated monomers (E) copolymerizable therewith. The method for producing a polymer compound according to any one of (2) to (4), wherein the ethylenically unsaturated monomer (F) is subjected to an addition reaction.
(6) Isocyanate group-containing ethylenically unsaturated monomer (B), ethylenically unsaturated monomer (D) containing a reactive functional group other than (B), and other ethylene copolymerizable therewith The hydroxyl group-containing benzoyl compound (A) is subjected to an addition reaction with an isocyanate group of a copolymer obtained by copolymerizing a mixture of a polymerizable unsaturated monomer (E), and an ethylenically unsaturated monomer capable of addition reaction with (D). The method for producing a polymer compound according to any one of the above (2) to (4), wherein the monomer (F) is subjected to an addition reaction.

(7) The manufacturing method of the high molecular compound as described in said (5) or (6) whose weight average molecular weights of the said high molecular compound are 5000-1 million.
(8) The above (5) to (5), wherein the hydroxyl group-containing benzoyl compound (A) is 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one 7) The manufacturing method of the high molecular compound in any one.
(9) Polyfunctional ethylenically unsaturated monomer containing two or more ethylenically unsaturated double bonds in one molecule with respect to the polymer compound described in any of (2) to (4) above A polymer composition comprising a body or an oligomer.

  The polymer compound of the present invention is used in a curing reaction by active energy such as ultraviolet rays, has a very efficient photocurability, generates very little odor during the curing reaction, can suppress deterioration of the working environment, and is excellent. A photocured product having excellent physical properties can be obtained.

この化合物は下記の一般式（ｃ）の化合物と一般式（ｄ）の化合物を反応させることに得ることができる。

The present invention will be described in detail below.
For the synthesis of the polymer compound of the present invention, a novel compound of an ethylenically unsaturated monomer (C) represented by the following general formula (a) is used.

This compound can be obtained by reacting the compound of the following general formula (c) with the compound of the general formula (d).

In the above reaction, the benzoyl compound has hydroxyl groups at both ends, but one carbon has two hydrogens and the other carbon has two alkyl groups, in which case the reaction has hydrogen. The hydroxyl group of the other carbon selectively reacts to obtain a monomer of the ethylenically unsaturated compound (C) represented by the general formula (a).
Specific examples of the hydroxyl group-containing benzoyl compound (A) used for the synthesis of the ethylenically unsaturated compound (C) of the present invention include 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2. -Methyl-1-propan-1-one, 1- [4- (2-hydroxymethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 1- [4- (2- Hydroxypropoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-ethyl-1-propane- 1-one etc. can be mentioned, and 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one is preferred.
Examples of the isocyanate group-containing ethylenically unsaturated monomer (B) used for the addition reaction with the hydroxyl group-containing benzoyl compound (A) include 2-isocyanatoethyl (meth) acrylate and 3-isocyanatopropyl (meth). An acrylate etc. can be mentioned.

The addition reaction is performed by adjusting the isocyanate group equivalent of the hydroxyl group-containing benzoyl compound and the isocyanate compound, mixing them, and heating in the presence of an organic acid, organic tin or other known hydrolysis catalyst generally used in the addition reaction. It can be done easily.
Specifically, 1 mol of an isocyanate group-containing ethylenically unsaturated monomer (B) is added to 1 mol of a hydroxyl group contained in a substituent of the benzoyl compound by an addition reaction. ) Can be synthesized. In addition, the production | generation of the ethylenically unsaturated monomer (C) obtained by the said addition reaction can be easily confirmed because the peak of an isocyanate group lose | disappears by IR (infrared absorption spectrum).

この式において、Ｒ_１、Ｒ_２及びＲ_３はそれぞれ独立に炭素数１〜４のアルキル基を表わし、ｍ、ｎは１〜３の整数を表す。
この高分子化合物は上記一般式（ａ）の化合物（Ｃ）とエチレン性不飽和単量体の共重合体を得、このエチレン性不飽和単量体のところに別のエチレン性不飽和単量体を付加反応させることにより製造することができる。 The polymer compound of the present invention is a novel polymer compound containing both one or more residues of the compound represented by the following general formula (b) and one or more ethylenically unsaturated double bonds in one molecule. is there.

In this formula, R ₁ , R ₂ and R ₃ each independently represent an alkyl group having 1 to 4 carbon atoms, and m and n each represent an integer of 1 to 3.
This polymer compound obtained a copolymer of the compound (C) of the above general formula (a) and an ethylenically unsaturated monomer, and another ethylenically unsaturated monomer at the ethylenically unsaturated monomer. It can be produced by addition reaction of the body.

This preferred production method is shown below.
(1) First, an ethylenically unsaturated monomer (C) having the above structure is obtained by an addition reaction between a hydroxyl group-containing benzoyl compound (A) and an isocyanate group-containing ethylenically unsaturated monomer (B). Next, a mixture of (C) and an ethylenically unsaturated monomer (D) containing a reactive functional group and another ethylenically unsaturated monomer (E) copolymerizable therewith is copolymerized. To obtain a copolymer, and an addition reaction of (D) of this copolymer with an ethylenically unsaturated monomer (F) capable of addition reaction.

Moreover, the following manufacturing methods can also be used.
(2) First, an isocyanate group-containing ethylenically unsaturated monomer (B), an ethylenically unsaturated monomer (D) containing a reactive functional group other than B, and other ethylenic monomers copolymerizable therewith. A mixture of unsaturated monomers (E) is copolymerized to obtain a copolymer, and then a hydroxyl group-containing benzoyl compound (A) is added to this isocyanate group, and (D) in the copolymer is further reacted. A production method in which an addition-reactive ethylenically unsaturated monomer (F) is subjected to an addition reaction.

First, compounds other than the above used in the synthesis will be described.
Ethylenically unsaturated monomer (D)
Examples of the ethylenically unsaturated monomer (D) containing a reactive functional group include (I) an isocyanate group-containing ethylenically unsaturated monomer, (II) a hydroxyl group-containing ethylenically unsaturated monomer, (III And glycidyl group-containing ethylenically unsaturated monomer and (IV) carboxyl group-containing ethylenically unsaturated monomer.
(I) As isocyanate group containing ethylenically unsaturated monomer, 2-isocyanatoethyl (meth) acrylate, 3-isocyanatopropyl (meth) acrylate, etc. can be mentioned. These isocyanate group-containing ethylenically unsaturated monomers can be used alone or in combination.

(II) Hydroxyl group-containing ethylenically unsaturated monomers include hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, polyethylene glycol monoacrylate, polypropylene glycol monoacrylate, polytetramethylene glycol monoacrylate, polyethylene glycol polytetramethylene Glycol monoacrylate, polypropylene glycol polytetramethylene glycol monoacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monomethacrylate, polytetramethylene glycol monomethacrylate, polyethyleneglycol Polytetramethylene glycol monomethacrylate, polypropylene glycol polytetramethylene glycol monomethacrylate, and the like. Preferred are hydroxyethyl acrylate and hydroxyethyl methacrylate. These hydroxyl group-containing ethylenically unsaturated monomers can be used alone or in combination.

(III) Glycidyl group-containing ethylenically unsaturated monomers include glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, methyl glycidyl acrylate, methyl glycidyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl And methacrylate. Glycidyl methacrylate is preferred. These glycidyl group-containing ethylenically unsaturated monomers can be used alone or in combination.
(IV) As the carboxyl group-containing ethylenically unsaturated monomer, acrylic acid, methacrylic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride, 2-methylmaleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid , Tetrahydrophthalic anhydride, their metal salts, ammonium salts or mixtures thereof. Acrylic acid, methacrylic acid, maleic acid, and maleic anhydride are preferred. These carboxyl group-containing ethylenically unsaturated monomers can be used alone or in combination.

Other ethylenically unsaturated monomers (E)
Other copolymerizable ethylenically unsaturated monomers (E) include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, allyl (meth) acrylate, Ethylene glycol di (meth) acrylate, methoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, acrylonitrile, styrene, styrene derivatives, vinyl acetate, vinyl propionate Vinyl chloride, vinylidene chloride, ethylene, propylene, butylene, isobutylene and the like can be used. These ethylenically unsaturated monomers can be used alone or in combination. The glass transition temperature of the self-photocurable resin composition of the present invention is not particularly limited.

Ethylenically unsaturated monomer (F)
As this monomer, the same compound as the above (D) is used, but it reacts with (D), and therefore the combination is determined depending on the relationship with the component (D).
Component (D) is an isocyanate group-containing ethylenically unsaturated monomer, a hydroxyl group-containing ethylenically unsaturated monomer, a carboxyl group-containing ethylenically unsaturated monomer, or a glycidyl group-containing ethylenically unsaturated monomer. Depending on the case, as (F), hydroxyl group-containing ethylenically unsaturated monomer, isocyanate group-containing ethylenically unsaturated monomer, glycidyl group-containing ethylenically unsaturated monomer, carboxyl corresponding to the above-mentioned order Mention may be made of group-containing ethylenically unsaturated monomers.

Next, a method for producing the polymer compound of the present invention will be described.
Manufacturing method (1)
An ethylenically unsaturated monomer (C), an ethylenically unsaturated monomer (D) containing a reactive functional group, and another ethylenically unsaturated monomer (E) copolymerizable therewith are mixed. To obtain a copolymer by copolymerization.
A polymerization initiator is used for this polymerization. The polymerization initiator is not particularly limited as long as it is usually used, and examples thereof include azobisisobutyronitrile, azobis (2-methylbutyronitrile), benzoyl peroxide and the like.
As the polymerization method, a method of batch polymerization and a method of polymerization while continuously supplying each component can be applied. The polymerization is usually carried out at a temperature of 30 to 150 ° C. with stirring.

The mixing ratio of the monomers (C), (D), and (E) in the copolymerization is as follows: (C) is 0.01 to 20 mol%, (D) is 0.1 to 70 mol%, and (E) is 10-99 mol% is preferable.
Even if (C) exceeds 20 mol%, the curability of the film and the physical properties of the film after curing are not improved. If it is less than 0.01 mol%, the curability of the film is lowered, and physical properties such as sufficient hardness and water resistance cannot be obtained.
Even if (D) exceeds 70 mol%, the curability of the film and the physical properties of the film after curing are not improved. If it is less than 0.1 mol%, the curability of the film is lowered, and physical properties such as sufficient hardness and water resistance cannot be obtained.
When (E) exceeds 99 mol%, the curability of the film is lowered, and physical properties such as sufficient hardness and water resistance cannot be obtained. If it is less than 10 mol%, the stability of the polymer solution is poor and gelation occurs with time.

Next, (F) is subjected to an addition reaction to the copolymer.
The amount of (F) is preferably 0.1 to 1 equivalent per 1 mol of (D). If it is less than 0.1 equivalent, curability is not sufficient.
This addition reaction can be easily performed by heating in the presence of a commonly used catalyst.
Manufacturing method (2)
First, an isocyanate group-containing ethylenically unsaturated monomer (B), an ethylenically unsaturated monomer (D) containing a reactive functional group, and other ethylenically unsaturated monomers copolymerizable therewith ( A copolymer is produced by copolymerizing the mixture of E).
Here, when the hydroxyl group-containing ethylenically unsaturated monomer (D) is mixed with the isocyanate group-containing monomer (B) and subjected to a polymerization reaction, the hydroxyl group and the isocyanate group undergo a crosslinking reaction during the polymerization reaction. Since it becomes high molecular weight and gels, it cannot be used.
Monomer (B), (D), (E) mixing ratio is 0.01-20 mol% for (B), 0.1-70 mol% for (D), and 10-99 mol% for (E). Is preferred.

(B) Even if it exceeds 20 mol%, the sclerosis | hardenability of a film | membrane and the physical property of the film | membrane after hardening are not improved. If it is less than 0.01 mol%, the curability of the film is lowered, and physical properties such as sufficient hardness and water resistance cannot be obtained.
(D) Even if it exceeds 70 mol%, the sclerosis | hardenability of a film | membrane and the physical property of the film | membrane after hardening are not improved. If it is less than 0.1 mol%, the curability of the film is lowered, and physical properties such as sufficient hardness and water resistance cannot be obtained.
(E) When it exceeds 99 mol%, the curability of the film is lowered, and physical properties such as sufficient hardness and water resistance cannot be obtained. If it is less than 10 mol%, the stability of the polymer solution is poor and gelation occurs with time.

For the copolymerization, the same polymerization initiator and polymerization method as in production method (1) can be used.
Next, the hydroxyl group-containing benzoyl compound (A) is subjected to an addition reaction with the isocyanate group of this copolymer, and further, an ethylenically unsaturated monomer (F) capable of addition reaction with (D) in the polymer is further subjected to an addition reaction. .
The amount of addition of (F) is preferably 0.1 to 1 equivalent per 1 mol of (D). If it is less than 0.1 equivalent, curability is not sufficient.
These addition reactions can be easily performed by heating in the presence of a commonly used catalyst.
Similarly, the addition reaction can be performed while supplying the monomers all at once or continuously.

When using the polymer compound of the present invention as a self-photocurable resin, in addition to the components described above, if necessary, other resins, photopolymerization accelerators, polymerization inhibitors, film forming aids, plasticizers, Known and commonly used additives such as preservatives, antifoaming agents, surfactants and the like can be conveniently selected and added within a range not impairing the object of the present invention.
The weight average molecular weight of the polymer compound is desirably 5,000 to 1,000,000. When a polymer compound is used as a self-photocurable resin, if the molecular weight is less than 5000, the hardness when photocured is greatly reduced. If it exceeds 1,000,000, the solution viscosity of the self-photocurable resin becomes high, so that it becomes difficult to apply to the substrate, and workability is greatly reduced.

  The polymer compound of the present invention can contain a polyfunctional ethylenically unsaturated monomer or oligomer containing two or more ethylenically unsaturated double bonds in one molecule. The curability can be further improved by adding these monomers and oligomers. The reason why there are two or more double bonds in one molecule is that when there is one double bond, there is no cross-linking between molecules, and the curability of the polymer compound of the present invention is not improved.

  Polyfunctional ethylenically unsaturated monomers or oligomers include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (Meth) acrylate, neopentyl glycol adipate di (meth) acrylate, hydroxypivalate neopentyl glycol (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone-modified dicyclopentenyl di (meth) acrylate, ethylene oxide-modified phosphorus Acid di (meth) acrylate, allylated cyclohexyl di (meth) acrylate, isocyanurate di (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol Tri (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, propionic acid modified Examples include dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and caprolactone-modified dipentaerythritol hexa (meth) acrylate. Examples of the oligomer include urethane acrylate, epoxy acrylate, and polyether acrylate. The use range of the polyfunctional unsaturated monomer or oligomer is preferably 300 parts by mass or less with respect to 100 parts by mass of the self-photocurable resin. They can be used alone or in combination.

Hereinafter, the present invention will be specifically described with reference to examples. In the following, “part” means “part by mass” and “%” means “% by mass”.
Preparation of test piece It was applied to a polyMMA plate with an 8 mil applicator and dried at 60 ° C. for 10 minutes. Using a UV irradiator (Ushio Electric Co., Ltd., ultra-high pressure mercury lamp USH-250SC), it was cured by irradiating with ultraviolet rays so as to have an integrated illuminance of 500 mJ / cm ² and evaluated by the following test.
Pencil hardness It measured based on JIS-K-5400 with the cured coating film coated on the polyMMA board.

Adhesiveness A cross cut was put into the cured coating film coated on the polyMMA plate, and cellotape (registered trademark) was pasted on the cut coating film. After leaving for 1 hour, this cello tape (registered trademark) was peeled off to evaluate the adhesion. The evaluation criteria were as follows.
○: No peeling at all Δ: Partial peeling away ×: Warm water resistance to peel off the entire surface A cured coating film coated on a polyMMA plate was immersed in warm water at 60 ° C. for 1 week. The evaluation criteria were as follows.
○: No change △: Partially whitened ×: Fully whitened

Solution viscosity The solution viscosity of the obtained self-photocurable resin was evaluated. The evaluation criteria were as follows.
○: Low viscosity and easy to handle Δ: Medium viscosity and somewhat difficult to handle ×: High viscosity and difficult to handle Weight average molecular weight measurement Using the GPC method, Shodex GPC KF-806 is used for the column, tetrahydrofuran is used as the eluent, and at room temperature It was measured.

(Production Example 1)
In a light-shielding reaction vessel equipped with a thermometer, stirring bar, reflux condenser, and dropping funnel, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane- 200 parts of 1-one, 0.2 parts of di-n-butyltin dilaurate and 0.04 parts of methoquinone were added and stirred and heated to 50 ° C. Here, 138.3 parts of 2-isocyanatoethyl (meth) acrylate was added dropwise over 1 hour, and the mixture was further stirred at 50 ° C. for 2 hours to obtain a photosensitized group-containing ethylenically unsaturated monomer A-1.

Example 1
In a light-shielding reaction vessel equipped with a thermometer, stirring rod, reflux condenser, and dropping funnel, 60 parts of dipropylene glycol dimethyl ether (trade name Proglide DMM, manufactured by Dow Chemical Co., Ltd.) is stirred and heated to 110 ° C. Then, Formulation Example 1 listed in Table 1 was added dropwise over 1.5 hours. One hour after the completion of dropping, 1 part of azobisisobutyronitrile and 3 parts of dipropylene glycol dimethyl ether were added, and the mixture was further stirred at 110 ° C. for 2 hours. After cooling the temperature to 80 ° C., 0.5 part of methoquinone and Formulation Example 2 described in Table 1 were added. After the addition of Formulation Example 2, the mixture was further stirred at 80 ° C. for 4 hours. Dipropylene glycol dimethyl ether was added and diluted with high stirring, and the mixture was cooled to room temperature to obtain a self-photocurable resin having a nonvolatile content of 25%.

(Examples 2 to 4)
As Examples 2 to 4, Formulation Example 1 and Formulation Example 2 in Example 1 were changed to the compositions shown in Table 1. Otherwise, the same operation as in Example 1 was performed to obtain a self-photocurable resin.
(Example 5)
As Example 5, the same operation as in Example 1 was performed except that 130 parts of pentaerythritol hexaacrylate was added to obtain a self-photocurable resin.
(Example 6)
In a light-shielding reaction vessel equipped with a thermometer, a stir bar, a reflux condenser, and a dropping funnel, 60 parts of dipropylene glycol dimethyl ether was stirred and heated to 110 ° C. Added dropwise over 5 hours. One hour after the completion of dropping, 1 part of azobisisobutyronitrile and 3 parts of dipropylene glycol dimethyl ether were added, and the mixture was further stirred at 110 ° C. for 2 hours. After cooling the temperature to 80 ° C., 0.5 part of methoquinone and Formulation Example 2 shown in Table 2 were added. After the addition of Formulation Example 2, the mixture was further stirred at 80 ° C. for 4 hours. Dipropylene glycol dimethyl ether was added and diluted with high stirring, and the mixture was cooled to room temperature to obtain a self-photocurable resin having a nonvolatile content of 25%.

(Examples 7 to 8)
As Examples 7 to 8, the compositions of Formulation Example 1 and Formulation Example 2 in Example 6 were changed to the compositions shown in Table 2. Otherwise, the same operation as in Example 6 was performed to obtain a self-photocurable resin.
Example 9
As Example 9, the same operation as in Example 6 was performed except that 130 parts of pentaerythritol hexaacrylate was added to obtain a self-photocurable resin.
(Comparative Example 1)
As Comparative Example 1, the same operation as in Example 1 was performed except that Formulation Example 2 in Example 1 was not used to obtain a resin.

(Comparative Example 2)
As Comparative Example 2, a resin was obtained in the same manner as in Example 1 except that Formulation Example 1 in Example 1 did not contain the A-1 solution.
(Comparative Example 3)
As Comparative Example 3, Formulation Example 1 and Formulation Example 2 in Example 1 were changed to the compositions shown in Table 3, and 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1 -14.36 parts of propan-1-one were added. Otherwise, the same operation as in Example 1 was performed to obtain a resin.

(Comparative Example 4)
As Comparative Example 4, the same operation as in Example 6 was performed except that Formulation Example 2 in Example 6 was not used, to obtain a resin.
(Comparative Examples 5-6)
As Comparative Examples 5 to 6, Formulation Example 2 in Example 6 was changed to the composition shown in Table 4. Otherwise by performing the same operations as in Example 6, a resin was obtained.
(Comparative Example 7)
As Comparative Example 7, Formulation Example 2 in Example 6 was changed to the composition shown in Table 4, and 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1 -Add 12 parts of ON. Otherwise, the same operation as in Example 6 was performed to obtain a resin.

(Example 10)
Production of ethylenically unsaturated monomer (C)
In a light-shielding reaction vessel equipped with a thermometer, stirring bar, reflux condenser, and dropping funnel, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane- 200 parts of 1-one, 0.2 parts of di-n-butyltin dilaurate and 0.04 parts of methoquinone were added and stirred and heated to 50 ° C. Here, 138.3 parts of 2-isocyanatoethyl (meth) acrylate was added dropwise over 1 hour, and the mixture was further stirred at 50 ° C. for 2 hours. Check the double bond peaks attributable to loss and 1638 cm ^-1 peak of isocyanate groups belonging to 2250 cm ^-1 by IR (infrared absorption spectrum) to give ethylenically unsaturated monomer (C).

  The polymer compound of the present invention is used in a curing reaction by active energy such as ultraviolet rays, has a very efficient photocurability, generates very little odor during the curing reaction, can suppress deterioration of the working environment, and is excellent. A photocured product having excellent physical properties can be obtained, and can be widely applied to applications requiring surface hardness, scratch resistance and chemical resistance, particularly as a coating material for coatings, coatings and inks.

Claims (9)

The following general formula (a)

A compound represented by Here, R ₁ , R ₂ and R ₃ each independently represents an alkyl group having 1 to 4 carbon atoms, and m and n are integers of 1 to 3. A polymer compound containing both one or more residues of a compound represented by the following general formula (b) and one or more ethylenically unsaturated double bonds in one molecule.

Here, R ₁ , R ₂ and R ₃ each independently represents an alkyl group having 1 to 4 carbon atoms, and m and n are integers of 1 to 3.   The polymer compound according to claim 2, wherein the polymer compound has a weight average molecular weight of 5,000 to 1,000,000.   The residue of the compound represented by the general formula (b) in one molecule is a photosensitizing functional group that generates radicals by active energy rays, and the polymer compound is a self-photocurable resin. The high molecular compound as described in.   Ethylenically unsaturated monomer (C) obtained by addition reaction of hydroxyl group-containing benzoyl compound (A) and isocyanate group-containing ethylenically unsaturated monomer (B), ethylenically unsaturated group containing reactive functional group The copolymer obtained by copolymerizing a saturated monomer (D) and a mixture of other ethylenically unsaturated monomers (E) copolymerizable therewith, into an ethylenic compound capable of addition reaction with (D) The method for producing a polymer compound according to any one of claims 2 to 4, wherein the unsaturated monomer (F) is subjected to an addition reaction.   Isocyanate group-containing ethylenically unsaturated monomer (B), ethylenically unsaturated monomer (D) containing a reactive functional group other than (B), and other ethylenically unsaturated monomers copolymerizable therewith An ethylenically unsaturated monomer capable of undergoing an addition reaction with (D) by adding a hydroxyl group-containing benzoyl compound (A) to an isocyanate group of a copolymer obtained by copolymerizing a mixture of monomers (E). The method for producing a polymer compound according to any one of claims 2 to 4, wherein F) is subjected to an addition reaction.   The method for producing a polymer compound according to claim 5 or 6, wherein the polymer compound has a weight average molecular weight of 5,000 to 1,000,000.   The hydroxyl group-containing benzoyl compound (A) is 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one. The manufacturing method of the high molecular compound of description.   A polyfunctional ethylenically unsaturated monomer or oligomer containing two or more ethylenically unsaturated double bonds in one molecule is blended with the polymer compound according to claim 2. A polymer composition.